Thermoplastics with good antistatic properties and improved processing properties

ABSTRACT

Disclosed are plastics compositions comprising thermoplastics, especially polyolefines, and a minor proportion of glycerine monoethers or glycerine monothioethers or substances derived therefrom. The new compositions possess in particular good antistatic properties and also improved processing and colour stability.

United States Patent Friedrich et al.

[4 1 Apr. 22, 1975 THERMOPLASTICS WITH GOOD ANTISTATIC PROPERTIES AND IMPROVED PROCESSING PROPERTIES Inventors: I'Ians-I-Ielmut Friedrich,

Philippstaal, Germany; Helmut Linhart, Reinach, Switzerland; Hermann Otto Wirth, Bensheim-Auerbach, Germany Assignee: Ciba-Geigy Corporation, Ardsley,

Filed: July 9, 1973 Appl. No.: 377,669

Foreign Application Priority Data July 11, 1972 Germany 2234016 May 17, 1973 Germany 2324888 U.S. (1260/4595 S; 260/33.2 R; 260/45.95 L;

260/77.5 SS; 260/94.9 GD; 260/836;

260/858; 260/830 P; 260/DIG. 15; 260/DIG. 21

Int. Cl. C08f 45/58 Field of Search 260/DIG. l5, DIG.21, 45.95 L, 260/45.95 S, 33.2 R, 94.9 GD, 77.5 SS, 836,

Primary Examiner-Melvyn I. Marquis Attorney, Agent, or Firm-Nestor W. Shust; Luther A. R. Hall 57 ABSTRACT Disclosed are plastics compositions comprising thermoplastics, especially polyolefines, and a minor proportion of glycerine monoethers or glycerine monothioethers or substances derived therefrom. The new compositions possess in particular good antistatic properties and also improved processing and colour stability.

10 Claims, N0 Drawings THERMOPLASTICS WITH GOOD ANTISTATIC PROPERTIES AND IMPROVED PROCESSING PROPERTIES The invention relates to plastics compositions and mouldings, films and fibres which can be manufactured therefrom, having good antistatic properties and improved processing and colour stability.

The thermoplastics concerned are thermoplastics such as polyolefines, polyamides, polystyrene and styrene copolymers, polyacrylonitrile, polyurethanes. polyesters, polyvinyl chlorides and polyacetals which acquire the improved properties mentioned through containing glycerine monoethers and substances derived therefrom.

lt is known that a reduction in the electrostatic charge of mouldings, films and fibres of thermoplastics can be achieved by addding to the plastic melt, during processing, substances which because of their specific incompatibility accumulate on the surface and because of their special structure increase the surface conductivity so greatly that spark formation, or dust attraction, resulting from becoming electrostatically charged no longer occur.

The antistatic agents for the finishing of thermoplastics which are used industrially all suffer from disadvantages and shortcomings which relate, in particular, to their inadequate chemical stability and above all heat stability.

The products of the amine type such as, for example, the fatty alkyl-(C -C )diethanolamines, impair the colour stability and light stability of the plastics provided therewith; in addition, their volatility is considerable. Finally, being amines, they are not physiologically harmless. Physiological harmlessness is a very critical point in antistatic agents, especially in those plastics which are employed for food stuff packagings. In accordance with the use for which they are intended, these substances accumulate at the surface of the plastic or are subequently applied thereto and are therefore exposed to increased extraction, especially by liquid foodstuffs. Thus, for example, the antistatic agent based on fatty alkyl-(C C d-diethanolamine has, according to the recommendations of the Plastics Commission of the BGA, been restricted to an added concentration of 0.1 percent, for example in polyethylene.

The effects of the polyglycol ethers and polyglycol esters are very weak and in addition characterised by inadequate intrinsic stability. This is also true of the partial esters of glycerine and other polyols.

Antistatics based on ate and onium salts in part show a good effect, but are not sufficiently stable at the processing temperatures which nowadays are very high; they lose their effect on decomposition.

It is the task of the present invention to develop antistatic agents which are characterised by a good effect, which furthermore possess a higher intrinsic stability and lower volatility and hence permit higher processing temperatures to be used for the appropriate thermoplastics, and which, not least of all, are distinguished by physiological harmlessness.

It has now been found that using glycerine monoethers and glycerine monothioethers and substances derived. therefrom it is possible to achieve, in thermoplastics, a substantially reduced electrostatic charge and, associated therewith, pronounced anti-fogging properties, this being true both of internal incorporation and external application.

Furthermore, these products impart to the thermoplastics increased stability on processing and produce a stabilisation of the substrate colour, that is to say prevent a discolouration, which is an additional advantage since themoplastics, particularly the polymers manufactured with ZlEGLER-NATTA catalysts, suffer degradation which cannot be eliminated entirely by antioxidants such as hindered phenols. This thermal degradation. which is recognisable, inter alia, from an increase in the melt index, utimately temperatures to a limitation of the processing temperatues and hence of the output during processing.

In addition to this thermo-oxidative degradation discolourations manifest themselves when processing such plastics, especially polyolefines, which cannot be prevented even by antioxidants.

It has now been found that these shortcomings can additionally be eliminated with the substances according to the invention.

The present invention therefore relates to antistatic thermoplastics which contain 0.01 5 percent by weight, preferably 0.05 2 percent by weight, relative to the thermoplastic, of a compound or mixtures of the formula I in which X denotes -O, Sor SO Y denotes n denotes the number 1 to 5, preferably 1 (for compounds) or, for statistical mixtures, 17 (as an average value) denotes a number between 0.5 and 8, preferably 1 to 3, and R, in the case of n 1 (individual compounds) denotes alkyl or phenylalkyl with 12 to 30 C atoms, preferably with l2 to 18 C atoms, which can be linear or have short chain branches of not more than 2 C atoms, and can be also be interrupted, preferably only once, by one or more different groups such as -O, S CO HC=CH, phenylene or or R, in the case of n 2 to 5 (individual compounds) or H 0.5 to 8 (mixtures), denotes alkyl with 8 to 30 C atoms, preferably with 12 to 18 C atoms, which can be linear or branched andcan also be interrupted, preferably only once, by O-, S CO HC=CH -or gc H phenylalkyl with an alkylene radical of l to 3 C atoms, preferably with 3 C atoms, which can addtionally be substituted at the phenyl nucleus by alkyl with up to 18 C atoms, with the entire radical having to contain a total of at least 9 C atoms, alkylphenyl with a total of 3,879,346 3 4 9 to 30 atoms, preferably 14 to 15 C atoms, alkoxypheproperties of these polymers through the content of a nyl with 3 to 12 C atoms in the alkyl radical, preferably hydrophilic polymer. 3 to 8 C atoms, alkoxycarbonylphenyl with 2 to l8 C Admittedly, US. Pat. No. 2,624,719 describes seconatoms in the alkyl radical, or cycloalkyl with a total of dary alcohols or ether-alcohols, such as, for example, 9 to 30 C atoms, preferably with 9 to 15 C atoms, and, 3-ethoxy-1 ,2-propanediol, as auxiliaries for improving optionally, in addition to further additives, at most 1 the colour of polystryrene. However, the products of percent by weight of hydrophilic polymers relative to the present invention are distinctly superior to these the thermoplastic, but preferably no hydrophilic polyadditives in this effect also.

mers. Examples of compounds according to the formula l The term short-chain branching denotes that the lin- 10 which re u ed a cording to the invention are: ear alkyl chain is substituted by one or more methyl or ethyl groups. "9 E Amongst the substances of the formula I, preferred OH OH substances are those in which X represents 0 or S, n represent 1 or 71 (as average value) represents a num- R1 Y n'tetradecyli n octadecyl ber between 1 and 5 and R represents unbranched alkyl ethylhexadecyli oley], zmethyl'uncosyli y i with 12 to 18 c atoms, alkylphenyl with 9 to 12 c iso-tetra-tridecyl, yh y -p y y atoms in the alkyl chain or alkylbenzyl with 9 to 12 C p y i y lohexyl-phenyl, t-butyl-phe y y atoms in the alkyl chain, and amongst those especially P y -p P y-p y y y'p y i the substances in which X 0 and R represents an un- W W'P W y y y 'p y branched alkyl with 12 13 C atoms octadecyloxycarbonyl-phenyl, 4-cyclohexyloxycarbo- Mixed products of the formula y -p y y y y i y y y octadecyl-cyclohexyl, n-dodecylS--CH CH nare particularly valuable. y 2 o 2C 2 Preferably, according to the present invention, polydodecyl-OCOCl l -CH S-CH -CH CH olefins, especially polypropylenes or high pressure polyethylenes, polyvinyl chlorides or polyurethanes are '9 provided with an antistatic finish. O OH Some of the substances used according to the application are previously known as compounds. However, R node yl, n-oc yl, -decyl, -heXadecyl, nthe use, disclosed here, as antistatic agents for thermoeicosyl, n-hexacosyl, iso-tridecyl, lplastics, is not previously known. octylOCOCl-l n-dodecyl-OCOCH ln Compt. Rend. 258 (26), 6,466 (1964), British Pat. n-octadecylOCO-CH iso- No. 1,029,610 and J. Org. Chem. 26,615 (1961), some octadecylOCOCH -Cl-l dodecyl-phenyl, representatives of these classes of compounds have aldodecyl-benzyl,

n-octadecyl-O-CH CH-CH n-tetradecyl-O-CH -CH-CH OH OH n-dodecy1-O-CH -0H-CH hexyl O-CH -C IH-CH OH OH ready been described. Furthemore, Belgian Pat. No. and 767,021 claims polycondensation products of glycidol with l,2-dihydroxyalkanes as detergents, especially for nonyl fl@ 4 cosmetics, with anionic catalysts serving as condensta- 2 I 2 0H tron agents.

In Belgian Pat. No. 767,020, polycondensation prodn-Alkyls as radicals of appropriate mercaptans which ucts of glycidol with mercaptans functions as intermeare obtainable analogously to the synthesis reaction dediate steps for sulphoxides which can be manufactured scribed by ZIEGLER for obtaining alcohols, starting therefrom, and the sulphoxides in turn can be used as from aluminium, hydrogen and ethylene, with subsecosmetic detergents. quent sulphurisation.

It is furthermore known, from US. Pat. No. 3,375,2l3to employ the synergistic combination ofhyl8 37 o(CH2 2 3 Q drophilic polymers with alkyl ethers and alkyl esters of H polyhydroxy compounds for improving the dyestuff receptivity of polyolefines.

It has now been found that the sole use of glycerine l2 25 2 g 3 5 monoethers and substances related thereto imparts to H thermoplastics a property independent therefrom, namely an antistatic property, without the additional 4 manifestation of the disadvantage of an unfavourable 2 2 3 2 effect on the mechanical properties and processing bu Further compounds of the formula I wherein n is greater than 1 are obtainable by isolation from the appropriate glycidolisation mixtures.

The following additives are preferred:

The compounds of the formula I are used as additives for thermoplastics. As such it is possible to use, for example:

1. Polymers which are derived from singly or'doubly unsaturated hydrocarbons, such as polyolefines such as, for example, polyethylene, which can optionally be crosslinked, polypropylene, polyisobutylene, polymethylbutene-l polymethylpentene-l, polybutene-l, polyisoprene, polybutadiene, polystyrene, polyisobutylene, copolymers of the monomers on which the said homopolymers are based, such as ethylene-propylene copolymers, propylene-isobutylene copolymers, stryrene-butadiene copolymers and terpolymers of ethylene and propylene with a diene such as, for example, hexadiene, dicyclopentadiene or ethylidenenorbornene, and mixtures of the abovementioned homopolymers such as, for example, mixtures of polypropylene and polyethylene, polypropylene and polybutene-l, and polypropylene and polyisobutylene.

2. Polyamides and copolyamides which are derived from diamines and dicarboxylic acids and/or from aminocarboxylic acids or the corresponding lactams, such as polyamide 6, polyamide 6/6, polyamide 6/10, polyamide ll and polyamide l2.

3. Polyesters which are derived from dicarboxylic acids and dialcohols and/or from hydroxycarboxylic acids or the corresponding lactones, such as polyethylene glycol terephthalate, and poly-1,4-dimethylolcyclohexane terephthalate.

4. Polyacrylonitrile as well as its copolymers with other vinyl compounds, such as acrylonitrile/- butadiene/styrene, acrylonitrile/styrene and acrylonitrile/styrene/acrylic ester copolymers.

5. Unplasticised also chlorinated polyvinyl chloride as well as unplasticised copolymers of vinyl chloride, for example with vinyl acetate, and mixtures of these polymers with other copolymers and chlorinated polyolefines with a predominant content of vinyl chloride in the total mixture.

6. Plasticised polyvinyl chloride, also using butadiene-acrylonitrile copolymers, provided the proportion of vinyl chloride in the total mixture predominates.

Possible plasticisers are:

Dibutyl phthalate, di-Z-ethylhexyl phthalate, dibutyl sebacate, tributyl acetyl-citrate, tri-Z-ethylhexyl acetylcitrate, diphenyl-2-ethylhexyl phosphate, alkylsulphonic acid esters (C 2120) of phenol and of the cresols, and also polymeric plasticisers such as adipic acid polyesters with 1,3-butanediol and hexanediol, and adipic acid polyesters with 1,3- and/or l,2-propanediol, of which the free OH groups are optionally acetylated.

7. Polyurethanes and polyureas.

8. Polyacetals, such as polyoxymethylene and polyoxyethylene, as well as polyoxymethylenes which contain ethylene oxide as the comonomer.

Together with the substances of the formula I used In the case of alcohols, mixtures of different levels of according to the invention, the thermoplastics can con glycidolisation are in principle obtained. However, by tain the customary additives used for the processing of using excess alcohol the reaction can be influenced in these polymers, such as plasticisers, heat-stabilisers, ana favour of the mono-reaction product, that is to say tioxidants, dyestuffs, fillers, lubricants and flameproofthe pure glycerine monoether. The excess alcohol is ing agents. Hydrophilic polymers such as, for example again removed during working up and added to the polyethylene oxides and substances related thereto next batch. should however at most be present in amounts of l per- A second method synthesis which is also known is via cent by weight relative to the thermoplastic. and prefepichlorohydrin: erably not be present at all, in order not to have an un- 10 favourable influence on the mechanical properties and C B "9 2' processing properties.

The substances according to the invention are incorporated into the substrates in a concentration of 0.0l to 5 percent by weight calculated relative to the matel5 rial to be processed. Preferably, 0.05 to 2, and es ecially preferentially 0.1 to 1.0 percent by weight of ihe 24 .49 2 2 substances are incorporated into the material. OH

The incorporation can be carried out after the polymerisation, for example by mixing the substances and optionally further additives into the melt in accordance with the methods customary in the art, before or during shaping. The substances can also be incorporated in the form of a master batch which contains these compounds, for example, in a concentration of 25 C 2.5 to 25 percent by weight, into the polymers to be 12 25 rendered antistatic. Further details of the method of incorporation can be found in Examples 8289.

In principle, the substances according to the inven- The chlorohydrin formed in the first stage yields the desired end product on alkaline saponification. For the preparation of glycerine monothioethers there is a second route via l-chloro-dihydroxypropane in accordance with the following equation:

tion can also be used for the provision of an external antistatic finish. In these cases, the substances can be v 2 25 2' 2 C1 applied in the dissolved state by dipping or spraying. OH OH Suitable solvents are, for example, ethanol, acetone, ethyl acetate and i-propanol, also mixed with water. This method can also be used in the phenol series. Even aqueous emulsions are suitable systems. A method of preparation for glycerine monothioeth- The preparation of the compounds of the formula I, ers by addition of mercaptan to glycerine monoallyl used according to the invention, in which n denotes l ethers, as formulated for a representative example:

. n I C H SH H C C11 Cll O CIl (EH OH OH C H -S-CH CH -Cl l -OCH (flI-EIH OH OH to 5, can be carried out according to various processes. deserves special mention. Advantageously, glycidol is used as the starting sub- A further type of compound is obtained by addition stance. of monothioglycerine to glycidyl ethers, as shown be- Phenols react under anionic conditions, at temperalow:

C H O-Cr{-SH -l- I iS-Cl- I -CIIH- iI-l 0 OH OH l O 11 O-CH ?HCH -S CH OH-$H OH OH OH tures below 100C, solely to form the glycerine mono- Compounds of the formula I wherein n is greater than ethers. The same is also true of mercaptans as shown 1 can be prepared from the corresponding glycidolisaby the following equation: tion products with H =2 to 5 by fractional molecular distillation or by chromatographic methods of separa- C' dH 2' tion, preferably by gel permeation chromatography.

In the products of the formula I used according to the invention in which? =0.5 to 8, that is to say in the case P -*OCOCH S-CH -1H"$ of mixtures, glycidolisation products are concerned.

' OH They represent an important part of the present invention and are obtainable according to the following generally reaction equation:

Here, statistical mixtures, with F as the average value of the particular degree of glycidolisation, are concerned. The distribution function An/n relative to n was not determined in more detail. Due to the distribution," which is subject to the laws of statistics, and which can barely be influenced through the reaction conditions, some starting product always remains in all the glycidolisation products, though the proportion of this starting product decreases with the degree of glycidolisation. a. The presence of the starting product does not interfere with the technical properties of these products with regard to their application, so that it is possible to dispense with the removal of the starting product.

In the case of the alcohols, such statistical mixtures are produced under all conditions, whilst in the case of mercaptans and phenols they are in particular produced under the conditions of anionic catalysis, at temperatures about 120C.

Such mixed products shown particularly advantageous antistatic effects. Evidently, the distribution has a very favourable influence on the migration phenomena which are decisive for the antistatic surface effect. It should be mentioned particularly that the antistatic finishes achievable therewith are furthermore distinguished by particular stability.

In the case of the glycidolisation derivatives which contain more than one glycidol structural unit in the molecule, two structual types, A and B, are possible:

I]. OH 2 If the glycidolisation is carried out as an open reaction sequence in reaction steps which are independent of one another, structural type A is preferred. If, however, the reaction is carried out in a closed reaction secompounds (benzene, chlorobenzene and dichlorobenzene), halogenated hydrocarbons such as, for example,

quence (in the sense of polymerisation or telomerisation), structural type B is formed. With certain limitations it is possible, through choice of the reaction conditions (catalyst and temperature), to steer the course of the reaction towards structural type A or structural type B.

In the case of alcohols, the glycidolisation, that is to say the reaction with glycidol, best takes place under cationic conditions, with tin-(IV) chloride as the catalyst. The reaction is advantageously carried out by adding the glycidol dropwise to the starting product to which catalyst has been added. However, other cationic types of catalyst, for example FRlEDEL-CRAFTS catalysts, perchlorates and onium salts also syncatalytic systems can also be employed successfully. The reaction can be carried out even at room temperature; it is strongly exothermic. Solvents are generally not required. Advantageously, a reaction temperature which is just above the melting point of the alcohol to be reacted, is used. Suitable solvents are inert aromatic sym-tetracholorethane or carbon disulphide.

The reaction products formed under such conditions preferably belong to structural type A. At temperatures above the formation of B is more strongly favoured.

In the case of phenols, cationic catalysts lead to sidereactions. Here, however, anionic type such as sodium hydroxide, sodium methylate, potassium t-butylate, sodium amide and similar systems can be employed. The first glycidolisation stage takes place even at temperatures below 100C. Under these conditions, however, a higher degree of glycidolisation (n I) is not possible. If the reaction is carried out, a priori, at a temperature of l l5l 30C, higher glycidolisation products can also be obtained. Under these conditions, the reaction products represent statistical mixtures also for n 1. In general, the use of a solvent can be dispensed with. However, where a solvent is used, high-boiling ethers such as anisole can above all be employed.

The reaction sequence which takes place under the conditions mentioned bears all the characteristics of a polymerisation. This means that structural type B is preferentially formed.

Both cationic and anionic catalysts can be used for the reaction of mercaptans. As in the case of the phenols, the reaction ends, at temperatures below 100C, at the first glycidolisation stage at which a single product has been formed. Higher glycidolisation products, these being in the form of statistical mixtures, can only be obtained at temperatures above C. Viewed in total, however, the anionic catalysts provide the more favourable course of the reaction.

Under these conditions the course of the reaction can again be described as a genuine polymerisation, which means that for 71 l reaction type B is preferentially formed.

The method described below is best for arriving at the statistical glycidolisation products in the case of X =SO2:

OH OH After conversion into the sulphone:

on on the further glycidolisation can be carried out as in the case of alcohols.

In principle, the conversion into the sulphone stage can also start from the glycidolisation product of a mercaptan, though difflculites can occur in working up, especially in the case of products with a higher degree of glycidolisation.

Examples of starting products for glycidolisation reactions have been listed below.

a. Alcohols: n-octanol, n-decanol, n-dodecanol, noctadecanol, i-octadecanol (2-ethyl-hexadecanol), oleyl alcohol, hexyldecanol 2-octyldodecanol, a technical Cal/C n-alkyl alcohol mixture, technical (In/C n-alkyl alcohol mixture, laurylbenzyl alcohol, 1,2-dihydroxydodecane, 1,Z-dihydroxy-octadecane, 3- phenylpropanol, 6-phenyl-hexanol, 2-hydroxyoctadecane, 2-hydroxy-dodecane, 1 l-hydroxyuncosane and 4-cyclohexanol.

b. Phenols: butylphenol, nonylphenol, dinonylphenol, laurylphenol, dilaurylphenol, hydroquinone monobutyl ether, resorcinol monohexyl ether, pcyclohexylphenol, t-octylphenol and 3- octadecyloxycarbonylphenol.

c. Mercaptans: octylmercaptan, dodecylmercaptan, t-dodecylmercaptan, octadecylmercaptan, thioglycolic acid lauryl ester, and Bmercaptopropionic acid stearyl ester, and also mercaptans which are obtainable analogously to the synthesis reaction described by ZIEGLER for the production of alcohols, starting from aluminum, hydrogen and ethylene, with subsequent sulphurisation.

Finally, the compounds according to the invention with n =1 can also serve as starting products, the glycidolisation advantageously being carried out cationically.

The invention is explained in more detail in the examples which follow. Percent therein denotes per cent by weight and parts therein denote parts by weight.

EXAMPLE 1 OH OH 1 1 CH (CH -O-CH CH"CH 3-(Tetracosyloxy)-propanediol-(1,2) 177 g of n-tetracosyl alcohol and 2 ml of tin tetrachloride are heated to 75C and 46.3 of epichlorohy-.

drin is added over the course of 30 minutes. The mixture is then stirred for a further 4 hours at 100C. After Yield: 155 g (72% of theory); melting point 85C C calculated 75.4%, found 75.2% H calculated 13.4%, found 13.2% calculated 11.2%, found 11.4%

EXAMPLE 2 OH OH I l CH (CH O-CH -CH-CH 3-( montanyloxy)-propanediol-( 1,2)

The synthesis is carried out under the conditions described in Example 1, using the following starting products and reagents: 205 g of montanyl alcohol (melting point: 84C), 46.3 g of epichlorohydrin, 2 ml of tin tetrachloride, 51 g of sodium formate and 200 ml of ethylene glycol.

Yield: 157 g (65% of theory); melting point 92C C calculated 76.8%, found 76.95% H calculated 13.3%, found 13.15% 0 calculated 9.9%, found 9.90%

EXAMPLE 3 OH (3H l CH (CH -S-CH CHr-CH Yield: melting point 93C found 73.55% found 12.70% found 6.65%

found 6.93%

191 g (81% of theory); C calculated 73.7%, H calculated 12.8%, 0 calculated 6.8%, S calculated 6.8%,

EXAMPLE 4.

OH OH 3'y-Octadecylmercapto-propoxy )-propanedioll ,2)

0.8 part of benzoyl peroxide is dissolved in 39.6 parts of glycerine l-allyl ether. 85.8 parts of octadecylmercaptan are added to this solution and thereafter the reaction mixture is warmed for 3 hours at C. 2 Phases form. The lower phase solidifies after cooling and is separated off and recrystallised from acetone.

EXAMPLE 8 Yield: 42 parts (33% of the wry); en'stalli -d melting point Sit-60C m P U 3 C 'l l' td 68.857. f d 67.9% H fril i llit ed 12.04%. r8321! 11.8% t H- H SCH CHCH S calculated 7.66%. found 7.5%

3-(B-Hydroxy-y-dodecyloxy-propylmercapto)- EXAMPLE 5 propanediol-( 1,2)

Cl-l -(CH O C-CH S-CH -CH C1-l "O-"C1'l CH-CH 3-[y-(Dodecyloxycarbonyl-methylmercapto)- 21.6 parts of thioglycerine and 0.2 part of sodium propoxyl]-propanediol-( 1,2) H methylate are warmed to 80C. Thereafter 48.5 parts 0.5 part of benzoyl peroxide is dissolved in 39.7 parts of dodecyl glycidyl ether are added dropwise at the of glycerine l-allyl ether. 78 parts of thioglycolic acid same temperature and the mixture is stirred for a furdodecyl ester are added dropwise to this solution. ther 2.5 hours, at 100C. The reaction product is re- Thereafter the mixture is stirred for a further hour at crystallised from petroleum ether (100140C). 80100C. The reaction product is not purified. 70

Yield: 62 parts (88% of theory); crystalline powder. Yield: 1 17.8 parts 100% of theory); colourless liquid, melting point 40- 44C n,,'-': 1.4783 S calculated 9.15%. found 8.9% S calculated 8.16%. found 8.2% OH calculated 14.56%. found 14.2%

EXAMPLE 6 EXAMPLE 9 1 CH 'fCH Q- O C-CH SCH -CH CH O-CH u l-CH 3-['y-(Octadecyloxycarbonyl-methylmercapto)- ro oxy]-propane l-(1.2) 35 or; +014 s-ca -ca -cn -o-cu cn-cn The synthesis is carried out under the conditions de- 3 2 ll 2 2 2 2 2 scnbeddm g a d g theffolllowlilg 3-'y-Dodeeylmercapto-proxy)-propanediol-( 1,2) ucts if I p g g g i y The synthesis is carried out under the conditions departs 0 10g a 10 if; 0cm 6826f i scribed in Example 5, using the following starting prodi benZo-v peroxl e reacnon pro uct 40 ucts and reagents: 66.1 parts of glycerine l-allyl ether, punfied' 101.2 parts of dodecylmercaptan and 0.5 of benzoyl peroxide. The end product was recrystallised from acetonitrile.

Yield: 143 parts 100% of theory); waxy consistency;

5 calculated 6.72% found 64% Yield: 102 parts (61% of theory); crystalline powder;

melting point 40-43 C S calculated 9.58%, found 9.4%

EXAMPLE 7 EXAMPLE 10 DH OH (?H (DH (11H l I 1-C H -O CCH -CH SCH -CH-CH C H (CH O-CH CH-CH S-cl-l2-CH-CH 3-[B-(2-i-Nonyloxycarbonyl)-ethylmercapto]- propanedioll ,2

46.5 parts of B-mercaptopropionic acid i-nonyl ester and 0.3 part of sodium methylate are warmed to 40C and 14.8 parts of glycerine-glycoidol are added in such a way that the temperature does not exceed 40C. The mixture is then stirred for a further 30 minutes, at 60C.

Yield: 61.2 parts of theory); yellow. viscous liquid; 11 1.4840 S calculated 10.46%, found 10.6%

Yield: 76 parts (87.5% of theory); crystalline powder;

melting point 60 63C 5 calculated 7.39%, found 7.4%

OH calculated 1 1.75%, found 1 1.5%

EXAMPLE 11 Yield: 99 parts (99% of theory): yellow, viscous liquid:

S calculated 9.6'71. found 9.4%

EXAMPLE 12 3-[B-(Octadecyloxycarbonyl-methylmercapto]- propanediol-( 1,2)

The synthesis is carried out under the conditions described in Example 7, using the following starting products and reagents: 103.3 parts of thioglycolic acid octadecyl ester, 22.2 parts of glycerine-glycidol and 0.3 35

part of sodium methylate. The reaction product is recrystallised from 500 ml of acetonitrile.

60 parts (48% of theory); melting point 5255C S calculated 7.6%. found 68% Yield:

EXAMPLES 13 -81 (Compare Table l) The conditions of preparation and physico-chemical criteria of all important glycidolisation products relating to the present invention are summarised in Table l. 50

The total OH content (total OH) is determined by acetylation and the vicinal OH content (vic. OH) is determined by splitting with periodic acid. In the case of the glycidolisation products of the mercaptans this method fails completely; in the case of the glycidolisa- 55 tion products of the phenols, problems can arise. A vapour pressure osmometer is sued for the molecular weight determination.

EXAMPLES 82 89 Antistatic Action specimens to acquire a charge, in the form of the charge level (mV), and the charge dissipation over the course of time, in the form of the half-life -the latter being an indirect measure of the surface resistance. Climatic conditions: 45 percent relative atomspheric humidity and 22C.

Within the scope of the test programme, comparison samples of known antistatic agents were also always tested simultaneously.

EXAMPLE 82 Test in Polypropylene Samples of the substances according to the invention are mixed into polypropylene powder (MFI 3-230C, 2.16) which in turn is stabilised with 0.2percent of a phenolic antioxidant, and the mixture is extruded in a single-screw extruder at 200-260C. Test specimens are taken from the pressed sheet first obtained and are tested after appropriate conditioning (45 percent atomspheric humidity and 22C). Table 2 contains the measured data thus obtained. The table also includes the effects achieved with known antistatic agents. The comparison shows the superiority of the substances according to the invention over commercially available products.

EXAMPLE 83 Test In Hlgh Pressure Polyethylene (ldpe) The substances to be tested are sprinkled onto a commercially available polyethylene of low density (MFl -l90C, 2.16). 0.2 mm thick cast films are produced from the dry blend mixtures at 160-200C on a customary extruder and these films are then subjected to the antistatic test. The measured data are summarised in Table 3.

It can be seen from this that even at very low concentrations of additive an excellent antistatic effect can be observed.

EXAMPLE 84 Test In Low Pressure Polyethylene (hdpe) Pressed sheets are manufactured by means of a single-screw extruder from a polyethylene of high density (MFI 7-l90C, 2.16 kg) provided with the customary additives, and after addition of the antistatic agent to be tested, and the test specimens taken from the pressed sheets are subjected to the electrostatic test. Table 4 provides information on the results thereby obtained.

The known antistatic based on fatty alkyl-(C, -C diethanolamine is admittedly comparable in effect with the substances according to the invention. The superiority of the latter is above all based on their colourstabilising effect which the amine product does not display.

EXAMPLE 85 Test In Polyurethane A 25 percent strength solution in dimethylformamide is prepared from the commercially available product ESTANE 5707, a linear single-component polyesterurethane. After addition of the antistatic agent to be tested, an 0.1 mm thick film is produced from this solution and, after prior drying at C, is subjected to the customary measuring process, using a polypropylene sheet, not provided with an antistatic finish, as the support for the test specimens in the measuring instrument.

The measured data thereby obtained are contained in Table 5.

EXAMPLE 86 Test In Polyacrylonitrile A percent strength solution in dimethylformamide is prepared with CRYLOR, a fibre-forming polyacrylonitrile, at 80C, ancl films 0.1 mm thick are prepared therefrom after addition of the antistatic agent to be tested. After drying at 140C, their electrostatic behaviour is examined under the same conditions as in the case of the polyurethane. The results are summarised in Table 6.

EXAMPLE 87 Test In Polyamide 6 20 EXAMPLE 88 Test In Plasticised Polyvinyl Chloride A mill hide is produced from a commercially available polyvinyl chloride, suspension type, K-value 70, on a laboratory mixing mill at 180C, using a mixing time of 5 minutes.

Formulation 100 parts of S-PVC (K-value 70) 55 parts of dioctyl phthalate 1 part of organo-tin/sulphur stabiliser (based on: 5 di-butyl-tin/bis-thioglycolic acid-i-octyl ester) 0.2 part of amide wax 2 parts of test substance (antistatic agent) The small test sheets taken from the mill hide are examined in a known manner for their electrostatic properties. Table 8 contains the measured data thereby obtained.

It should here be noted additionally that the substances according to the invention do not have an adverse influence on the heat stability of the PVC.

EXAMPLE 89 Test In Unplasticised Polyvinyl Chloride A tape 1 mm thick and 40 mm wide is produced from a commercially available polyvinyl chloride, suspension type, K-value 65, by means of a single-screw extruder and slit die, at 200C material temperature. Formulation 100 parts of S-PVC (K-value 1.5 parts of organo-tin/sulphur stabiliser (based on: di-n-butyl-tin/bis-thioglycolic acid-i-octyl ester) 0.2 part of montan wax 1.5 parts of lubricant (based on: synthetic wax ester) 2.0 parts of test substance (antistatic agent) The small test sheets taken from the extruded tape are tested in a known manner for their electrostatic properties. Table 9 provides information on the measured data thereby obtained.

As already mentioned, the substances according to the invention have no adverse influence on the heat stability of the PVC, at least not on the initial colour.

EXAMPLE Effect On the Processing Stability The processing-stabilising effect of the substances according to the invention in various grades of polypropylene is tested by measuring the melt index, at 230C and 2.16 kg load, on multiple extrusion in a singlescrew extruder. The substances are incorporated at 260C and rpm.

The change in the melt index after 1, 3 and 5 extrusions can be seen in Table 10. Glycerine monostearyl ester is employed as the comparison substance. The effect of the substances according to the invention is superior to that of glycerine monostearyl ester.

EXAMPLE 91 Intrinsic Thermal Stability Finally, the intrinsic thermal stability of the compounds and substances according to the invention is also examined in comparison to commercially available products.

The test is carried out in an open glass test tube (internal diameter 2.5 mm) using a silicone bath which can be heated electrically. Bubble formation is used as the criterion of decomposition. Should a discolouration occur at the same time, this is also recorded.

After determining the decomposition range at a relatively high speed of heating, the actual decomposition temperature is determined at a speed of heating of 2C per minute (starting about 50C below the decomposition temperature found in the preliminary experiment).

The results are summarised in Table 1 1.

Table 1 Conditions of synthesis and physico-chcmical criteria of the glycidolisation products of alcohols, phenols, mercaptans and sulphones (calculated values are shown in parentheses) (Examples 13-81) Exam- Starting product Dcgrcc Conditions Analytical data Properties pic of glyof synthc- (consistcncy) No. cidolisis 7r total OH 7: vic. OH Molecular sation, C ata- Tcmpweight n lyst era- 13 nOctanol 1 SnCL, I 65 16.3 (16.6) 9.0 (16.6) 183 (204) n,, ":1.4486

15 n-Dodccanol 1 SnCl, 65 12.3 (13.1) 7.7 (13.1) 271 (260) semi-solid Table 1 Contmued Conditions of synthesis and physico-chemical criteria of the glycidolisation products of alcohols. phenols, mcrcaptans and sulphones (calculated values are shown in parentheses) (Examples 13-81) Exam- Starting product Degree Conditions Analytical data Properties ple of glyof synthe- (consistency) No. cidolisis 7: total OH 71 vic. OH Molecular sation. C ata- Tempweight n lyst erature.

16 3 65 16.8 (16.6) 7.0 7.8) 397 (409) highly viscous 17 65 19.5 (18.3) 9.5 6.1) 590 (557) liquids 18 n-Pcndadecanol 1 SnCL, 65 10.6 (1 1.2) 6.6 1 1.2) M.p. 43-50 19 3 65 15.0 15.1) 7.3 7.1) 460 (451) M.p. 4l-50 20 n-Octadccanol 0.5 SnCl 65 3.6 5.0) 270 (307) M.p. 54-59 21 0.75 65 7.9 9.1) 3.8 7.4) M.p. 55-60 Mixture:

28 {n-Eicosanol l SnCL, 70 8.0 (-88) 4.2 (-88) M.p. 55-63 29 n-Docosanol 3 70 12.8 12.7) 6.8 (-6.4) M.p. 55- 63 Mixture:

30 {n-Tetraeosanol 1 SnCl 75 Solubility too low to permit M.p. 6570 31 n-Hcxacosanol 3 75 determinations M.p. 50-65 32 2-Hexyl-decanol 3 SnCl 65 13.5 (14.6) 8.7 7.3) viscous liquid 33 5 65 15.1 (16.7) 6.6( 5.6) highly viscous mass 34 2-Octy1-dodecanol 3 SnCl 65 11.1 (13.1) 6.6 6.5) viscous li uid 35 5 65 13.1 (15.3) 5.5 5.1) hi ghly viscous mass 36 Z-Ethy'lhexadecanol 1 SnCl 65 9.8 9.9) 4.9( 9.9) n,, ":1.4600

37 Olcyl alcohol 1 SnCl 65 10.0( 9.9) 6.1 9.9) n,, ":1.47O1

40 5 65 15.1 (16.0) 6.1 5.3) highly zviscous 41 6 65 16.0 (16.7) 5.4 4.8) liquids 42 1.2-Dihydroxy- 2 SnCL, 65 l 1.9 (1 1.7) 8.1 7.8) highly visdodecane ous mass 43 Dodecyl-bcnzyl 1 SnCL, 71) 9.4 9.7) 5.6 9.7) 355 (351) Waxy alcohol 44 4 70 13.5 (14.8) 6.4 5.9) masses 45 3-Phenylpropanoll SnCl, 65 16.2 (16.9) 8.9 (16.9) 189 (200) yiscous l iquid 46 3 65 18.3 (19.0) 9.4 9.5) semi-solid mass 47 1.2-Dihydroxydo- 1 SnCL, 65 18.0 (18.4) 6.9 12.3) 290 (276) semi-solid dccane mass 48 1.2 Dihydroxyocta- 2 SnCL, 65 14.8 (15.7) 7.8 7.8) 470 (435) M.p. 60-65" dccane 49 Butylphenol 1 NaNH 120 15.6 15.9) 220 (214) viscous liquid 50 3 NaOMc 120 19.0 (18.8) 390 (362) highly viscous mass 51 Nonylphcnol 1 NaOMe 120 11.9 (11.6) 12.1 (11.6) n,, 1.5165

52 3 120 15.5 (15.4) 505 (443) viscous liquid 53 5 120 17.4 17.3) highly vis- 54 8 120 17.9 (18.8) cous masses 55 Dinonylphenol l NaOMc 120 8.3 8.1) 440 (421) yisctzlus 56 4 120 13.8 (13.2) 6.0 5.3) highly viscous 57 7 120 16.3 (15.7) 4.5 3.9) 920 (865) masses 58 Dodecylphenol 2 K- 120 12.6 (12.4) 9.7 8.3) 450 (411) viscous 59 n-Dodecylmercaptan 1 SnCl; 80 l 1.6 (12.3) 287 (276) M.p. 4048 60 3 90 15.3 (16.0) 456 (425) semi-solid fpaste-like 61 3 NaOMe 120 16.2 (16.0) 440 (425) masses 63 n-Octadecyl- 0.75 NaOMc 120 7.5 7.5) M.p. 5568 mercaptan 67 t-Dodccylmercaptan 3 NaOMe 120 16.5 (16.0) ,F": 1.4960

68 n-Dccylmercaptan 2 13F,, 15.2 (15.8) 315 (322) semi-solid paste-like 69 3 70 16.5 (17.2) masses 7O 4 70 17.9(l8.'l) 490(471) Test substance corresponding added concnarge hglf-life to Example centration l-vel sec] AY 21V] R: n-doiecyl a; O ,5 620 l R: n-hexedecyl a; O .5 900 C .6

n-octadecyl 0.5 55-0 0.3

OH I v n R. C H CH CH CH 8 1.0 550 0.0

R: i-n0.".ylS-COCZ'I -CH 7 0.5 l, 350

F'.: ndodecylC'CO-CH 11 O .5 1,000 0.5

R: n-0cteciecyl-O-CG-CH 12 0.5 760 C c" R. C E-1 O Cri h CH 2.0 JUO O 5 35 known substances Table 2 (Example 83) Antistatic effect in high pressure polyethylene (ldpe) LSt substance corresponding added concharge half-life to Example centretion level [sec] lmV None i 1,100 i 'Ob52Cih-u\..2 OH OH R: n-octadecyl a; 0.1 0.3

g R CH C n 0H OH OH i R: n-hexacosyl 3 0.2 160 C -3 5i known substances Test substance corresponding added concharge half-life to Example centration level [see frzvl v R-O-(-Ch -C H -O-%h R: n-octadecyl H: 1 22 0.5 500 0.5

I E: 2 2a 0.5 500 0.5

Antistatic effect in polyacr-yloni'trile corresponding added concharge level= half-life to Example centration [mVj I [sec] (5) g l, GOO .20

I i I I 5-: i 1.0 1 56:1 1.; z V 1 i l R: dodecyl f1: 5 61 i 1.0 i 00 0 .5

4 E e I I on 0H 1 i lR: n-octedecyl l .0 550 E 0 .5 I I I 92 known substances Table 7 Antistatic effect in polyarnide 6 (Example 87.)

Test substance corresponding added concharge half-life to Example centration level [sec] [311"]. None i 1,200 I 60 I ,p I r\ v A 0 0111 0 0% 0H I R: dodecylphenyl f1: 2 58 2.0 1,000 5 R: dodecyl I: 5 17 2.0 900 2 R O m 2 H OH OH R: noctadecyl 2.0 1,100 6 R: n-hexaciecyl X 2.0 1,100 Q z: knovm substances Table 8 (Example 88) Antistatic effect in plasticised polyvinyl chloride Test substance corresponding added concharge halfl1le to Example centration level ec] Rene 400 0.3

= L" u 3 O cH C :1: octcclecyl n. 25 2.0 120 0.3

octaczccyl f1. 5 61 2.0 100 0.5

R: dodec l-benzyl F1- 5 76 2.0 130 0.5

W A c. 2 TH 011 OH CH 3: cctaciecyl X 9: 2.0 170 0.3

octadecyl X -5 2.0 '70 0.5

known substances lip-152 Antistatic effect in unplas'ticised polyvinyl chloride (Example 89) Test substance corresponding added concharge half-life to Example centration level [sec] None 1,000

R-O'CH --C H -O H R: octadecyl i 5 2.0 1.0

oleyl f1. 6 +1 2.0 560 1.1

R: nonylphenyl f1: 8 54 2.0 0.8

R-D -Cr1 -Cl H3-OI !H R: dodecyl 5. 62 2.0 520 1.1

is; octadecyl n: 66 2.0 420 0.5 a: dodecyl-benzyl 5 I 77 2.0 490 0.7

Table 10 (Example 90) Effect on the processing stability of polypropylene Test substance corresponding 1 melt indie-es. after extrusions (added concentration: 0.5%) to Example 1 3 I 5 None 5a 1 R- C JL- 2. ..2 up!) Oi.

R: n-octadecyl i; 1 22 4. 6.2 7.9

R: nonylphenyl a: 1 51 6.1 I 9 .O

R-SQCI--Cg--OI-I o3; i

R: n-cctadecyl a: 5 5 .1 7.5 10 .O

RO-CH (:JH=CH OH a; n-octadecyl 5-: 4.1 7.2 10.5 i

R: (lodecy1S4CI- 9 ;.5 6 l 8.1 2 known substances 1 Test substance corresponding melt indices after extrusions (added concentration: 0.5%) to Exernole 5 R-S--CH CHCH & 4 OH OH R: n-octadecyl x 4.1 7.5 12.5

--- 4 1 R SO ch 5 O%H R: dodecyl T1: 5 '79 -..5 8.0 10.8

as known substances Table 11 (Example 91) Decomposition temperatures of substances according to the invention and of known antistatic agents 5a knovm substances Test substance corresponding decomposition decomposition criteria to Example temperature bubble discolour- C) formation xation RXCH -(IH-(\Ih OH OH R: n-octadecyl Si 255 R: n-tetracosanyl l 260 R: n-octadecyl 235 R-O{-CH2C'2H3O%H R: n-octadecyl Y1: l 22 2 'rO R: 2-hexy1-decy1 F1: 5 52 265 R: ncnylphenyl n: 3 52 190 5 Y R S Ch Gigi 0% OH I R: n-octadecyl f1: 1 6 2A0 i R: n-dodecyl 1 1: 3 51 255 R: dodecylbenzyl "f1: 2 210 Test substance corresponding decomposition decomposition criteria to Example ,tempcrature bubble discolour- C formation action Known products Product based on stcaric acid dicthanolamidc 130 Lauric acid polyethylcnc glycol ester (molecular weight: 400) I70 Cationic product based on fatty alkylaminc 170 Cationic product based on fatty alkylaminc 220 Anionic product based on fatty alkyl sulphonatc 160 Product based on fatty alkylpolyethylene glycol ethcr I Product based on quaternary fatty alkyl-ammonium compound 200 Product based on quaternary fatty alkyl-ammonium compound 120 Product based on nonylphcnol polyethylene glycol ethcr What we claim is:

l. Antistatic thermoplastics which contain 0.01 to 5 per cent by weight, relative to the thermoplastic, of a compound or mixtures of the formula I in which X denotes O, Sor SO Y denotes CH- CH-CH l 2 CH OI OH OH or R, in the case of n =2 to 5 or r7 =0.5 to 8, denotes alkyl with 8 to 30 C atoms which may be linear or branched and can also be interrupted by O, S, CO -HC=l-lC-or phenylalkyl with an alkylene radical of l to 3 C atoms which can additionally be substituted at the phenyl nucleus by alkyl with up to 18 C atoms, with the total radical having tohave at least 9 Catoms, alkylphenyl with 9 3OC atoms, alkoxyphenyl with 3 to 12 C atoms in the alkyl radical, alkoxycarbonylphenyl with 2 to 18 carbon atoms in the alkyl radical or alkylated cyclohexyl with 9 to 30 C atoms and, optionally in addition to further additives, at most 1 per cent by weight of hydrophilic polymers, relative to the thermoplastic,

2. Antistatic thermoplastics according to claim 1, characterised in that they do not contain any hydrophilic polymers as additives.

3. Antistatic thermoplastics according to claim 1, characterised in that the thermoplastic is a polyolefine.

4. Antistatic thermoplastics according to claim 3, characterised in that the polyolefine is polypropylene or high pressure polyethylene.

5. Antistatic thermoplastics according to claim 1, characterised in that the thermoplastic is polyvinyl chloride.

6. Antisatic thermoplastics according to claim 1, characterised in that the thermoplastic is a polyurethane.

7. Antistatic thermoplastics according to claim 1, characterised in that they contain substances of the formula (l) in which Y represents CH- CH-CH l l 2 (3H2 or OH OH X represents O--or S, 5 represents] or n (as an average value) represents a number between 1 to 5 and R represents unbranched alkyl with 12 to 18 C atoms, alkylbenzyl with 9 to 12 C atoms in the alkyl chain.

8. Antistatic thermoplastics according to claim 1, characterised in that they contain substances of the formula (l) in which Y represents CH- CHCH CH or H OH '2 X represents 0, n represents 1 or H (as an average value) represents a number between 1 and 5 and R represents unbranched alkyl with 12 to 18 C atoms.

9. 'Antistatic thermoplastics according to' claim 1, characterised in that they contain mixtures of the for mula 10. Antistatic thermoplastics according to claim I, characterised in that they contain substances of the formula (I) in amounts of 0.05 to 2 percent by weight relative to the thermoplastic. 

1. ANTISTATIC THERMOPLASTICS WHICH CONTAINS 0.01 TO 5 PER CENT BY WEIGHT, RELATIVE TO THE THERMOPLASTIC, OF A COMPOUND OR MIXTURES OF THE FORMULA I
 1. Antistatic thermoplastics which contain 0.01 to 5 per cent by weight, relative to the thermoplastic, of a compound or mixtures of the formUla I R-X-(CH2-Y-O)nH (I) in which X denotes -O-S-or -SO2, Y denotes
 2. Antistatic thermoplastics according to claim 1, characterised in that they do not contain any hydrophilic polymers as additives.
 3. Antistatic thermoplastics according to claim 1, characterised in that the thermoplastic is a polyolefine.
 4. Antistatic thermoplastics according to claim 3, characterised in that the polyolefine is polypropylene or high pressure polyethylene.
 5. Antistatic thermoplastics according to claim 1, characterised in that the thermoplastic is polyvinyl chloride.
 6. Antisatic thermoplastics according to claim 1, characterised in that the thermoplastic is a polyurethane.
 7. Antistatic thermoplastics according to claim 1, characterised in that they contain substances of the formula (I) in which Y represents
 8. Antistatic thermoplastics according to claim 1, characterised in that they contain substances of the formula (I) in which Y represents
 9. Antistatic thermoplastics according to claim 1, characterised in that they contain mixtures of the formula 